Tetradecahalocyclohexasilane compounds, such as those represented by the formula YmSi6X14-nX′n (Y=cations with a +1 charge and m=2, or a +2 charge and m=1; and X and X′=F, Cl, Br, I and n=0-13) are important intermediates in the production of cyclohexasilane, Si6H12, and other silane compounds. Cyclohexasilane can be employed as a liquid precursor for electronics grade silicon materials and devices. Cyclohexasilane is a relatively benign, liquid phase alternative to gaseous SiH4 and/or corrosive trichlorosilane (HSiCl3) in the various processes and technologies adopted in silicon-based electronic industries. Existing methods of producing the Y2Si6Cl14 intermediate salt typically use nucleophilic organic amines as ligands. Such syntheses are prone to extensive side reactions that deplete useful starting materials and give low yields of the intermediate Y2Si6Cl14 salt (typically approximately 10%).